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@ARTICLE{Akola:151456,
author = {Akola, J. and Kohara, S. and Ohara, K. and Fujiwara, A. and
Watanabe, Y. and Masuno, A. and Usuki, T. and Kubo, T. and
Nakahira, A. and Nitta, K. and Uruga, T. and Weber, J. K. R.
and Benmore, C. J.},
title = {{N}etwork topology for the formation of solvated electrons
in binary {C}a{O}-{A}l$_{2}${O}$_{3}$ composition glasses},
journal = {Proceedings of the National Academy of Sciences of the
United States of America},
volume = {110},
number = {25},
issn = {1091-6490},
address = {Washington, DC},
publisher = {Academy},
reportid = {FZJ-2014-01402},
pages = {10129 - 10134},
year = {2013},
abstract = {Glass formation in the CaO–Al2O3 system represents an
important phenomenon because it does not contain typical
network-forming cations. We have produced structural models
of CaO–Al2O3 glasses using combined density functional
theory–reverse Monte Carlo simulations and obtained
structures that reproduce experiments (X-ray and neutron
diffraction, extended X-ray absorption fine structure) and
result in cohesive energies close to the crystalline ground
states. The O–Ca and O–Al coordination numbers are
similar in the eutectic 64 mol $\%$ CaO (64CaO) glass
[comparable to 12CaO·7Al2O3 (C12A7)], and the glass
structure comprises a topologically disordered cage network
with large-sized rings. This topologically disordered
network is the signature of the high glass-forming ability
of 64CaO glass and high viscosity in the melt. Analysis of
the electronic structure reveals that the atomic charges for
Al are comparable to those for Ca, and the bond strength of
Al–O is stronger than that of Ca–O, indicating that
oxygen is more weakly bound by cations in CaO-rich glass.
The analysis shows that the lowest unoccupied molecular
orbitals occurs in cavity sites, suggesting that the C12A7
electride glass [Kim SW, Shimoyama T, Hosono H (2011)
Science 333(6038):71–74] synthesized from a strongly
reduced high-temperature melt can host solvated electrons
and bipolarons. Calculations of 64CaO glass structures with
few subtracted oxygen atoms (additional electrons) confirm
this observation. The comparable atomic charges and
coordination of the cations promote more efficient elemental
mixing, and this is the origin of the extended cage
structure and hosted solvated (trapped) electrons in the
C12A7 glass.},
cin = {PGI-1 / IAS-1},
ddc = {000},
cid = {I:(DE-Juel1)PGI-1-20110106 / I:(DE-Juel1)IAS-1-20090406},
pnm = {422 - Spin-based and quantum information (POF2-422)},
pid = {G:(DE-HGF)POF2-422},
typ = {PUB:(DE-HGF)16},
UT = {WOS:000321500200033},
pubmed = {pmid:23723350},
doi = {10.1073/pnas.1300908110},
url = {https://juser.fz-juelich.de/record/151456},
}